Operando Electrochemical Atomic Force Microscopy of Solid–Electrolyte Interphase Formation on Graphite Anodes: The Evolution of SEI Morphology and Mechanical Properties

[Image: see text] Understanding and ultimately controlling the properties of the solid–electrolyte interphase (SEI) layer at the graphite anode/liquid electrolyte boundary are of great significance for maximizing the performance and lifetime of lithium-ion batteries (LIBs). However, comprehensive in situ monitoring of SEI formation and evolution, alongside measurement of the corresponding mechanical properties, is challenging due to the limitations of the characterization techniques commonly used. This work provides a new insight into SEI formation during the first lithiation and delithiation of graphite battery anodes using operando electrochemical atomic force microscopy (EC-AFM). Highly oriented pyrolytic graphite (HOPG) is investigated first as a model system, exhibiting unique morphological and nanomechanical behavior dependent on the various electrolytes and commercially relevant additives used. Then, to validate these findings with respect to real-world battery electrodes, operando EC-AFM of individual graphite particles like those in commercial systems are studied. Vinylene carbonate (VC) and fluoroethylene carbonate (FEC) are shown to be effective additives to enhance SEI layer stability in 1 M LiPF(6)/ethylene carbonate/ethyl methyl carbonate (EC/EMC) electrolytes, attributed to their role in improving its structure, density, and mechanical strength. This work therefore presents an unambiguous picture of SEI formation in a real battery environment, contributes a comprehensive insight into SEI formation of electrode materials, and provides a visible understanding of the influence of electrolyte additives on SEI formation.